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Ferroelectric hafnia is one of the most promising materials for next generation of non-volatile memory devices. Several strategies have demonstrated to be of interest to improve its functional properties. Interface engineering, realized by the introduction of additional layer in the capacitor structure, is demonstrated as a promising strategy. However, interface layers can have multiple implications, such as changes in the chemistry of the interfaces and an increase of depolarization field, whose effects are difficult to discriminate. The role of HfO2 and ZrO2 capping is explored on polarization, retention, endurance, and leakage properties of Hf0.5Zr0.5O2 epitaxial films. In HfO2 capped films, lower polarization is observed, and endurance and retention are also comparably worse than in ZrO2 capped films. Complementary under illumination ferroelectric characterization and capacitance measurements indicate a reduction of defects and interface capacitance contribution in ZrO2 capped films. For both cappings, the interfaces with the Hf0.5Zr0.5O2 layer are shown to be compositionally sharp and the phase of Hf0.5Zr0.5O2 (HZO) grains is replicated on the capping layer, indicating that electrostatic effects prevail and that the use of interface layers with high permittivity, here ZrO2, is crucial to favor good functional properties.

An all-atom Molecular Dynamics (MD) study was applied to three viral nanoparticles (VLPs) of Turnip mosaic virus (TuMV), a potyvirus: the particles genetically functionalized with two peptides, VIP (human vasoactive intestinal peptide) and VEGFR (peptide derived from the human receptor 3 of the vascular endothelial growth factor), and the non-functionalized VLP. Previous experimental results showed that VIP-VLP was the only construct of the three that was not viable. VLPs subjected to our MD study were modeled by four complete turns of the particle involving 35 subunits of the coat protein (CP). The MD simulations showed differences in structures and interaction energies associated to the crucial contribution of the disordered N-terminal arms of CP to the global stability of the particle. These differences suggested an overall stability greater in VEGFR-VLP and smaller in VIP-VLP as compared to the unfunctionalized VLP. Our novel MD study of potyviral VLPs revealed essential clues about structure and interactions of these assembled protein particles and suggests that the computational prediction of the viability of VLPs can be a valuable contribution in the field of viral nanobiotechnology.

Inelastic interactions between a small, intense dipole and a weak, neutral monopole in two-dimensional flows are analysed. The neutral vortex has vanishing exterior potential flow and the interactions involve the rotational flow of the vortices. It is shown that dipoles of small-size but large-amplitude, relative to the neutral vortex, may cross the vortex and scatter while leave the vortex stable

This study focuses on characterizing a discontinuity within the Seán stalagmite (4.75-7.75 cm) by means of two nondestructive techniques: (1) high-resolution micro-computed tomography (micro-CT) and (2) X-ray fluorescence (XRF) core scanning (XRFCS). Micro-CT was used to study the stalagmite density, and XRFCS was applied to obtain the qualitative elemental composition and colour measurements. The new data obtained from nondestructive techniques have been combined with previously published geochemical data and fabric determinations from the same stalagmite found in Sa Balma des Quartó cave in Mallorca. The two methodologies applied in the present study have improved the characterization of the distinctive horizon. The micro-CT images identified the layer as a minor event due the high air content. The distinctive horizon is characterized by a high Ti-content, indicating the arrival of terrigenous particles. Based on those observations, together with the fact that the micrite layer appears filling the gaps between the older columnar fabric, we argue that the micrite layer may represent a major flooding event inside the cave after the year 1616 ± 23 CE and before the year 1623 ± 28 CE, which can be related to an extreme rainfall event. This hypothesis is further supported by the observed cave flooding during the autumn of 2018.

The advancement of ecosystem-based management of aquatic ecosystems should no longer be limited by a lack of tools. However, a lack of comprehensive understanding of the capabilities of existing tools can form a barrier for uptake. With this chapter, we strive to more fully describe one of these tools, the spatial-temporal ecosystem model Ecospace, which is part of the Ecopath with Ecosim (EwE) ecosystem modeling approach and software. Changes and developments in Ecospace have been faster than documented in recent years. Many features of Ecospace, including the most recent that have not been described before, are detailed in this chapter. The applications highlighted showcase the multitude of uses of the spatial application of EwE, which, especially due to expansion of the capabilities to incorporate the effects of environmental change, has facilitated its use outside of fisheries management to protection of biodiversity, ecosystem restoration and environmental impact assessment. New applications of Ecospace can truly contribute to advance modeling of cumulative impacts and management alternatives in marine ecosystems, and can be of interest to inform sectoral and intersectoral policy

Effects of high-pressure shift freezing (HPSF) at 200 MPa/-20 °C on physical, functional and thermal properties of egg white and egg yolk from three egg types were studied. The phase transition time in HPSF was shorter compared to atmospheric freezing (about 25% for egg yolk and 56% for egg white) due to the high degree of supercooling. The effect of freezing on functional properties seems to be related to different degrees of protein denaturation depending of the freezing/pressure level. Partial protein unfolding (suggested by higher free sulfhydryl) was observed after freezing at atmospheric pressure, especially for egg yolk. On the other hand, higher protein aggregation due to lower thermal denaturation enthalpy (50% in egg yolk and 70% in egg white) was found in HPSF samples, supported by decrease of protein solubility, disappear of electrophoretic bands and increase in viscoelasticity (G′ and G″ values).

Granzymes (Gzms), a family of serine proteases, expressed by immune and nonimmune cells, present perforin-dependent and independent intracellular and extracellular functions. When released in the extracellular space, GzmA, with trypsin-like activity, is involved in the pathophysiology of different inflammatory diseases. However, there are no validated specific systems to detect active forms of extracellular GzmA, making it difficult to assess its biological relevance and potential use as a biomarker. Here, we have developed fluorescence-energy resonance-transfer (FRET)-based peptide probes (FAM-peptide-DABCYL) to specifically detect GzmA activity in tissue samples and biological fluids in both mouse and human samples during inflammatory diseases. An initial probe was developed and incubated with GzmA and different proteases like GzmB and others with similar cleavage specificity as GzmA like GzmK, thrombin, trypsin, kallikrein, or plasmin. After measuring fluorescence, the probe showed very good specificity and sensitivity for human and mouse GzmA when compared to GzmB, its closest homologue GzmK, and with thrombin. The specificity of this probe was further refined by incubating the samples in a coated plate with a GzmA-specific antibody before adding the probe. The results show a high specific detection of soluble GzmA even when compared with other soluble proteases with very similar cleavage specificity like thrombin, GzmK, trypsin, kallikrein, or plasmin, which shows nearly no fluorescence signal. The high specific detection of GzmA was validated, showing that using pure proteins and serum and tissue samples from GzmA-deficient mice presented a significant reduction in the signal compared with WT mice. The utility of this system in humans was confirmed, showing that GzmA activity was significantly higher in serum samples from septic patients in comparison with healthy donors. Our results present a new immunoprobe with utility to detect extracellular GzmA activity

Uplift and unroofing of Jurassic-Cretaceous, mantle and crust, arc- and plume-related rock units in the Median Belt of the Dominican Republic exposed basement rocks with a protracted record of tectono-thermal events delineating the evolution of the northern edge of the Caribbean plate. In this article we focus on crustal rock units in the north-eastern half of the Median Belt. First Ar/Ar dating of metamorphic ferri-winchite (86.4 ± 2.5 Ma; crystallization date) and albite (82.3 ± 5.8 and 79.8 ± 1.6 Ma; cooling dates) in metabasites of boninitic photolith from the Aptian-Albian Maimón Formation in the Ozama shear zone points to a tectono-metamorphic event in the Upper Cretaceous. Beltwide, this event caused syn-metamorphic N- to NNE-directed, simple-shear dominated, mylonitic and phyllonitic deformation of the Maimón Formation at peak metamorphic conditions of 8.2 kbar and 380°C. Such conditions are consistent with subduction of a coherent portion of forearc (represented by the Maimón Formation) to depths of ~25-29 km. The tectono-metamorphic event dated here overlaps with the inception of Turonian-Coniacian SW-dipping subduction and metamorphic sole formation in a back-arc position recorded in the Moa-Baracoa ophiolite complex in neighboring Eastern Cuba. Contemporaneity between the subduction inception of forearc and back-arc portions of the Caribbean arc and the main pulse of plume activity recorded in the Caribbean Large Igneous Province (CLIP) suggests that plume activity promoted general plate instability leading to a regional-scale plate reorganization. This mantle-plume-induced plate margin reorganization was coeval with the inception of the NE-dipping subduction of the Farallón plate beneath Central America leading to the definition of the Caribbean Plate by double-verging subduction zones along its northern and southwestern margins.

In this work, we have investigated the performance of a 4H–SiC radiation sensor in the temperature range from 25 °C to 450 °C to explore its compatibility as detector of fast ion losses in plasma diagnostic of future nuclear fusion reactors. To simulate the escape of fusion-born alpha particles in D-T (deuterium-tritium) fusion plasmas, spectroscopic measurements were carried out in a vacuum chamber by irradiating the detector with a 3.5 MeV alpha beam from a Tandem accelerator. The detector was found to have an energy resolution ≤2% over the entire temperature range analyzed. Relevantly, the excellent spectrometric capabilities of the device have allowed us to calculate from experimental data, with unprecedented accuracy, the average energy required to create a single electron-hole pair in 4H–SiC as a function of temperature.

A theoretical study of the interaction between melamine and CO was carried out using density functional theory (DFT) with the B3LYP-D3(BJ)/aug-cc-pVTZ level of theory. The presence of anions interacting with melamine transforms the weakly bonded tetrel complexes into adducts. Thus, melamine acts as an FLP (frustrated Lewis pair) with acid groups (NHs as hydrogen bond donors) and a base group (N of the triazine ring). The application of the relative energy gradient formalism (REG) along the reaction coordinate has demonstrated that the ability of the melamine-anion systems to capture CO is linked to its capacity to polarize the CO molecule. These results have been confirmed by placing the melamine:CO complex in a uniform electric field with different strengths.

Understanding plant immune responses is complex because of the high interdependence among biological processes in homeostatic networks. Hence, the integration of environmental cues causes network rewiring that interferes with defense responses. Similarly, plants retain molecular signatures configured under abiotic stress periods to rapidly respond to recurrent stress, and these can alter immunity. Metabolome changes imposed by abiotic stressors are persistent, although their impact on defense remains to be clarified. In this study, we profiled metabolomes of Arabidopsis plants under several abiotic stress treatments applied individually or simultaneously to capture temporal trajectories in metabolite composition during adverse conditions and recovery. Further systemic analysis was performed to address the relevance of metabolome changes and extract central features to be tested in planta. Our results demonstrate irreversibility in major fractions of metabolome changes as a general pattern in response to abiotic stress periods. Functional analysis of metabolomes and co-abundance networks points to convergence in the reconfiguration of organic acid and secondary metabolite metabolism. Arabidopsis mutant lines for components related to these metabolic pathways showed altered defense capacities against different pathogens. Collectively, our data suggest that sustained metabolome changes configured in adverse environments can act as modulators of immune responses and provide evidence for a new layer of regulation in plant defense.

Hadron therapy is a radiotherapy modality which offers a precise energy deposition to the tumors and a dose reduction to healthy tissue as compared to conventional methods. However, methods for real-time monitoring are required to ensure that the radiation dose is deposited on the target. The IRIS group of IFIC-Valencia developed a Compton camera prototype for this purpose, intending to image the Prompt Gammas emitted by the tissue during irradiation. The system detectors are composed of Lanthanum (III) bromide scintillator crystals coupled to silicon photomultipliers. After an initial characterization in the laboratory, in order to assess the system capabilities for future experiments in proton therapy centers, different tests were carried out in two facilities: PARTREC (Groningen, The Netherlands) and the CNA cyclotron (Sevilla, Spain). Characterization studies performed at PARTREC indicated that the detectors linearity was improved with respect to the previous version and an energy resolution of 5.2 % FWHM at 511 keV was achieved. Moreover, the imaging capabilities of the system were evaluated with a line source of 68Ge and a point-like source of 241Am-9Be. Images at 4.439 MeV were obtained from irradiation of a graphite target with an 18 MeV proton beam at CNA, to perform a study of the system potential to detect shifts at different intensities. In this sense, the system was able to distinguish 1 mm variations in the target position at different beam current intensities for measurement times of 1800 and 600 s.

This work explores the potential of obtaining high-resolution thermal infrared (TIR) data provided by the Sentinel-2 (S2) & Sentinel-3 (S3) constellation in a typical semiarid agricultural environment. Maps of land surface temperature (LST) with 10–20 m spatial resolution were obtained from the synergy S2–S3 in the Barrax test site in Spain, for a set of 14 different dates in the summers of 2018–2019. Ground measurements of LST transects covering a variety of croplands and surface conditions were used for a ground validation of the disaggregation approaches. A cross validation of the LST products was also conducted using Landsat-8/TIRS images. Two recent approaches exploiting the linkages between shortwave and thermal data were adapted and tested, with differences in the inputs, the physical-mathematical framework, or the treatment of the LST residuals, and two options for the original 1 km S3 LST data were considered. Despite the large range of temperatures registered (295–330 K), differences with observed values resulted in an average RMSE < 3.0 K and a negligible systematic deviation, showing good results even in small fields ∼1 ha. Results confirm the need for appropriate adjustment techniques of the LST residuals obtained to better capture the low temperature conditions. The systematic overestimations introduced by the use of the operational sea and land surface temperature radiometer L2 LST product, and the limitations associated with certain irrigation management are discussed. Results in this work offer a solution to the lack of high-resolution satellite TIR data, and provide new opportunities for LST applications in agricultural areas.

Geochemical data of the Variscan gneisses derived from pre-Variscan intrusives and late-Variscan granitoids in the Pyrenees and the Catalan Coastal Ranges were obtained from two main sources: (1) individually mined from published articles and unpublished PhD theses (Autran et al., 1970; Guitard, 1970; Enrique, 1989; Soler and Enrique, 1989; Enrique, 1990; Soler, 1990; Gleizes, 1992; Debon et al., 1996; Arranz, 1997; Guitard et al., 1998b, 1998b; Roberts et al., 2000; Vilà et al., 2005; Casas et al., 2010; Navidad et al., 2010; Druguet et al., 2014; Laumonier et al., 2015; Navidad et al., 2018; Lemirre et al., 2019; Álvaro et al., 2021; Liesa et al., 2021; Casas et al., 2024), and (2) the GEOROC Database (Geochemistry of Rocks of the Oceans and Continents, Göttingen University, https://georoc.eu/; last access: 03/2024; Lehnert et al., 2000). Other Findable, Accessible, Interoperable, and Reusable (FAIR; Wilkinson et al., 2016) databases were searched using geographic and lithogeochemical constrains, yielding no results. The mined data were curated and classified based on the analysed rock types, ages, regional tectonic setting, and mode of occurrence in outcrop, resulting in more than 600 entries that are associated with up to 66 data fields. Associated with each entry are generic, descriptive and informative fields (Sample ID, Unit/Massif, Rock category, Rock details, Outcrop description, and References), major element oxide abundances (SiO2, Al2O3, FeOT, Fe2O3T, MnO, MgO, CaO, Na2O, K2O, TiO2, P2O5, and LOI), and trace element concentrations (Ag, As, Ba, Be, Bi, Co, Cr, Cs, Cu, Ga, Ge, Hf, In, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, Tl, U, V, W, Y, Zn, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu). The resulting database, named NEIGRA (North-East Iberian GRAnitoids), represents the first Open-Access compilation of granite and orthogneiss geochemical data in the Pyrenees and the Catalan Coastal Ranges.

Lumped-element kinetic inductance detectors (LEKIDs) based on sawtooth inductors for W -band are presented in this article. A careful analysis is carried out for the cross-polarization in the inductor geometry, which brings out the absorption of the nondesired E -field component of an incident wave plane. The proposed inductor geometry with sawtooth sections demonstrates improved cross-polarization. The analytical results are verified by comparison with 3-D electromagnetic (EM) simulations. As the first proof of concept, W -band optical response is demonstrated through quasioptical characterization at room temperature of an aluminum LEKID array. Moreover, a LEKID array based on bilayer superconducting titanium/aluminum (Ti/Al) thin film is developed for evaluating the performance at millikelvin temperatures. Darkness characterization confirms the high-quality factor of the fabricated detectors and the low-frequency design reliability. In addition, cryogenic optical experiments are performed for spectroscopic and detector sensitivity characterization. The proposed geometry opens the possibility of developing large-format polarimetric cameras based on on-chip LEKID structures for future astronomical experiments.

Directionally solidified Al2O3/Y3Al5O12 (YAG), Al2O3/YAG/ZrO2, Al2O3/GdAlO3 (GAP), Al2O3/GAP/ZrO2 and Al2O3/ZrO2 eutectic/non eutectic ceramics were prepared with laser zone melting. Their microstructure, phase component and shape were investigated. The results indicated that the molar ratio of Zr4+ to rare earth ions (Y3+, Gd3+) in the ZrO2 phase of the ternary eutectic was closed to 2:1. The free energy of chemical reaction was the key to determine the precipitation order of phase. The growth of the firstly-precipitated phase could be divided into the formation of ordered Bravais lattice composed by the oxygen ions, the diffusion of metal cations in this lattice and the change of phase morphology. The unfilled cation gap might be a fast channel for the ion transport. On the same growth plane, the nucleation of the later-precipitated phase began only after the firstly-precipitated phase was fully formed. The triangular was the main ion arrangement way for the stable nucleation and growth of phases. The effects of the precipitation temperature, the phase size, the eutectic type and the growth rate on the microstructure were discussed. This improved theory provided a more reasonable explanation for the formation of rod-shaped, layered, triangular, Chinese script (CS) and cellular microstructures, which might be of significance to regulate the morphology of microstructures.

Antarctica is one of the most outstanding analogs of Mars, and cyanobacterial mats are considered one of the most resilient biological consortia. The purpose of this study is to find out the effect of the Martian conditions on an Antarctic cyanobacterial mat. We exposed an Antarctic microbial mat to Martian conditions in a simulating chamber (MARTE) for 15 d and investigated the variations in the consortium by the use of 16S rRNA gene expression as an indicator of the biological activity. Metabarcoding using the V3-V4 regions of the 16S rRNA gene was used to determine the succession of the active members of the microbial consortium during the experiment. The results showed that the microbial mat, far from collapsing, can survive the stringent conditions in the simulating chamber. Different behaviors were displayed depending on the metabolic capabilities and physiological characteristics of every taxon. The main conclusion is that the Martian conditions did not impair growth in some of the groups, and thus, the investigated Antarctic community would be able to survive in a Martian environment at least during the short experimental period, although elements of the community were affected in different ways.

Liquid crystal elastomer (LCE)-based soft actuators are being studied for their significant shape-changing abilities when they are exposed to heat or light. Nevertheless, their relatively slow response compared with soft magnetic materials limits their application possibilities. Integration of magnetic responsiveness with LCEs has been previously attempted; however, the LCE response is typically jeopardized in high volumes of magnetic microparticles (MMPs). Here, a multistimuli, magnetically active LCE (MLCE), capable of producing programmable and multimodal actuation, is presented. The MLCE, composed of MMPs within an LCE matrix, is generated through extrusion-based 4D printing that enables digital control of mesogen orientation even at a 1:1 (LCE:MMPs) weight ratio, a challenging task to accomplish with other methods. The printed actuators can significantly deform when thermally actuated as well as exhibit fast response to magnetic fields. When combining thermal and magnetic stimuli, modes of actuation inaccessible with only one input are achieved. For instance, the actuator is reconfigured into various states by using the heat-mediated LCE response, followed by subsequent magnetic addressing. The multistimuli capabilities of the MLCE composite expand its applicability where common LCE actuators face limitations in speed and precision. To illustrate, a beam-steering device developed by using these materials is presented.

[Background] The study of plant photosynthesis is essential for productivity and yield. Thanks to the development of high-throughput phenotyping (HTP) facilities, based on chlorophyll fluorescence imaging, photosynthetic traits can be measured in a reliable, reproducible and efficient manner. In most state-of-the-art HTP platforms, these traits are automatedly analyzed at individual plant level, but information at leaf level is often restricted by the use of manual annotation. Automated leaf tracking over time is therefore highly desired. Methods for tracking individual leaves are still uncommon, convoluted, or require large datasets. Hence, applications and libraries with different techniques are required. New phenotyping platforms are initiated now more frequently than ever; however, the application of advanced computer vision techniques, such as convolutional neural networks, is still growing at a slow pace. Here, we provide a method for leaf segmentation and tracking through the fine-tuning of Mask R-CNN and intersection over union as a solution for leaf tracking on top-down images of plants. We also provide datasets and code for training and testing on both detection and tracking of individual leaves, aiming to stimulate the community to expand the current methodologies on this topic., [Results] We tested the results for detection and segmentation on 523 Arabidopsis thaliana leaves at three different stages of development from which we obtained a mean F-score of 0.956 on detection and 0.844 on segmentation overlap through the intersection over union (IoU). On the tracking side, we tested nine different plants with 191 leaves. A total of 161 leaves were tracked without issues, accounting to a total of 84.29% correct tracking, and a Higher Order Tracking Accuracy (HOTA) of 0.846. In our case study, leaf age and leaf order influenced photosynthetic capacity and photosynthetic response to light treatments. Leaf-dependent photosynthesis varies according to the genetic background., [Conclusion] The method provided is robust for leaf tracking on top-down images. Although one of the strong components of the method is the low requirement in training data to achieve a good base result (based on fine-tuning), most of the tracking issues found could be solved by expanding the training dataset for the Mask R-CNN model.

Anisotropic planar polaritons - hybrid electromagnetic modes mediated by phonons, plasmons, or excitons - in biaxial two-dimensional (2D) van der Waals crystals have attracted significant attention due to their fundamental physics and potential nanophotonic applications. In this Perspective, we review the properties of planar hyperbolic polaritons and the variety of methods that can be used to experimentally tune them. We argue that such natural, planar hyperbolic media should be fairly common in biaxial and uniaxial 2D and 1D van der Waals crystals, and identify the untapped opportunities they could enable for functional (i.e. ferromagnetic, ferroelectric, and piezoelectric) polaritons. Lastly, we provide our perspectives on the technological applications of such planar hyperbolic polaritons.

Milk yield and composition phenotypes are systematically recorded across several lactations in goats, but the majority of genome-wide association studies (GWAS) performed so far have rather ignored the longitudinal nature of such data. Here, we have used two different GWAS approaches to analyse data from three lactations recorded in Murciano-Granadina goats. In Analysis 1, independent GWAS have been carried out for each trait and lactation, while a single longitudinal GWAS, jointly considering all data, has been performed in Analysis 2. In both analyses, genome-wide significant QTL for lactose percentage on chromosome 2 (129.77–131.01 Mb) and for milk protein percentage on the chromosome 6 (74.8–94.6 Mb) casein gene cluster region were detected. In Analysis 1, several QTL were not replicated in all three lactations, possibly due to the existence of lactation-specific genetic determinants. In Analysis 2, we identified several genome-wide significant QTL related to milk yield and protein content that were not uncovered in Analysis 1. The increased number of QTL identified in Analysis 2 suggests that the longitudinal GWAS is particularly well suited for the genetic analysis of dairy traits. Moreover, our data confirm that variability within or close to the casein complex is the main genetic determinant of milk protein percentage in Murciano-Granadina goats.

We report the mesomorphic behaviour, dielectric and ferroelectric properties, and computational modelling of binary mixtures containing two bent-core liquid crystals: the so-called NG75-COO (3,4́- Bis[4-(4-n-tetradecyloxybenzoyloxy)benzoyloxy]biphenyl), which forms smectic phases, and IP31- AzB (3,4′ - Bis[4-(4-n-tetradecyloxyphenylazo)benzoyloxy]biphenyl), which forms columnar phases. The phase diagram, assessed by polarised optical microscopy, shows that the binary mixtures retain the mesophase behaviour of the major component, whilst the equimolar mixture displays smectic-type phases. Dielectric and ferroelectric analyses were carried out on samples containing 10%, 50%, and 90% of IP31-AzB (molar %), and we also investigated structure–property correlations by differential functional theory. The NG75-COO/IP31-AzB mixtures undergo strong dielectric and ferroelectric response due to the presence of highly polarisable groups in the bent-core components, particularly at the ester groups. All the mixtures under study exhibit light-responsiveness induced by reversible E-to-Z photoisomerization (trans-to-cis) of the azobenzene group in IP31-AzB, together with an increase in the molecular dipole moment. The potential to tune the phase behaviour of the mixtures, as well as their dielectric and ferroelectric responses, are investigated by light irradiation under different conditions of intensity and temperature.

Hydrophobic deep eutectic solvents (DESs), a recent class of green solvents, offer 100% atom economy, low cost, potential biodegradability, negligible toxicity and promising bioactivities. In this work, novel aroma-based therapeutic hydrophobic DESs were prepared and dispersed in aqueous media as nanoemulsions to potentiate biomedical applications, where polar media is encountered. A reusable microengineered stainless-steel isoporous membrane was fabricated by laser drilling technique. Three hydrophobic DESs, namely DES A (menthol and vanillin), DES B (menthol and raspberry ketone), and DES C (thymol and raspberry ketone) were prepared and emulsified in aqueous media by sustainable membrane emulsification technique. The optimised nanoemulsion (DES C-in-water) exhibited a monomodal size distribution with Zavg (size average) of 147 nm and polydispersity index of 0.22. From the application perspective, the formulated DES-in-water nanoemulsions and their constituents were evaluated for their antibacterial properties against Escherichia coli and Staphylococcus aureus. Additionally, antifungal properties of the DES-based emulsions were reported for the first time by testing them against four fungal strains, Aspergillus fumigatus, Candida albicans, Candida krusei, and Trichophyton mentagrophytes. The nanoemulsions were found to be exhibit antimicrobial effect and lesser quantities of individual compounds were needed in nanoemulsified state to show similar effects. Different 1D and 2D NMR techniques were successfully used to investigate the structural orientation and the inter and intramolecular interactions in the DES and emulsion systems, which revealed a probable cause for higher antimicrobial activity of DES C-based emulsions compared to its peers. Lastly, a synergistic effect of the components in nanoemulsions led to enhanced antimicrobial activities.

Hepatic thioredoxin domain-containing 5 (TXNDC5) is a member of the protein disulfide isomerase family found associated with anti-steatotic properties of squalene and located in the endoplasmic reticulum and in lipid droplets. Considering that the latter are involved in hepatic squalene accumulation, the present research was aimed to investigate the role of TXNDC5 on hepatic squalene management in mice and in the AML12 hepatic cell line. Wild-type and TXNDC5-deficient (KO) mice were fed Western diets with or without 1% squalene supplementation for 6 weeks. In males, but not in females, absence of TXNDC5 blocked hepatic, but not duodenal, squalene accumulation. Hepatic lipid droplets were isolated and characterized using label-free LC-MS/MS analysis. TXNDC5 accumulated in this subcellular compartment of mice receiving squalene and was absent in TXNDC5-KO male mice. The latter mice were unable to store squalene in lipid droplets. CALR and APMAP were some of the proteins that responded to the squalene administration in all studied conditions. CALR and APMAP were positively associated with lipid droplets in the presence of squalene and they were decreased by the absence of TXNDC5. The increased squalene content was reproduced in vitro using AML12 cells incubated with squalene-loaded nanoparticles and this effect was not observed in an engineered cell line lacking TXNDC5. The phenomenon was also present when incubated in the presence of a squalene epoxidase inhibitor, suggesting a mechanism of squalene exocytosis involving CALR and APMAP. In conclusion, squalene accumulation in hepatic lipid droplets is sex-dependent on TXNDC5 that blocks its secretion.

Ethylene/ethane separation is a critical and energy-consuming process in the chemical industry due to the similar properties of the compounds and the great need of ethylene for e.g., polymer production. Many materials have been studied for their implementation as membranes as an energetically favorable alternative to conventional distillation and adsorption processes. Metal-organic frameworks (MOF) have revealed promising properties as highly permeable and selective membranes. Among the most studied and promising MOF candidates is ZIF-8, known for its thermal stability and small pores connected by narrow-sized windows. In this work, we present an analysis of the influence of parameters such as temperature, feed pressure and feed flowrate on the separation of ethylene/ethane through a thin ZIF-8/alumina disc membrane. We observed that the temperature has a significant effect on the separation. The ethylene permeance increased with decreased temperature and reached 8.1 × 10−7 mol/(m2·s·Pa) at −30 °C. At this temperature, the ethylene/ethane selectivity was 2.5. The study concluded with a considerable enhancement of the permeance of ZIF-8 membranes for ethylene/ethane separations, while maintaining a good selectivity compared to the reported values in the literature. The results have important implications for the development of more cost-effective and energy-efficient membrane-based separation technologies for ethylene purification.

Performing nanoscale scanning electron paramagnetic resonance (EPR) requires three essential ingredients: First, a static magnetic field together with field gradients to Zeeman split the electronic energy levels with spatial resolution; second, a radio frequency (rf) magnetic field capable of inducing spin transitions; finally, a sensitive detection method to quantify the energy absorbed by spins. This is usually achieved by combining externally applied magnetic fields with inductive coils or cavities, fluorescent defects, or scanning probes. Here, we theoretically propose the realization of an EPR scanning sensor merging all three characteristics into a single device: the vortex core stabilized in ferromagnetic thin-film discs. On one hand, the vortex ground state generates a significant static magnetic field and field gradients. On the other hand, the precessional motion of the vortex core around its equilibrium position produces a circularly polarized oscillating magnetic field, which is enough to produce spin transitions. Finally, the spin–magnon coupling broadens the vortex gyrotropic frequency, suggesting a direct measure of the presence of unpaired electrons. Moreover, the vortex core can be displaced by simply using external magnetic fields of a few mT, enabling EPR scanning microscopy with large spatial resolution. Our numerical simulations show that, by using low damping magnets, it is theoretically possible to detect single spins located on the disc’s surface. Vortex nanocavities could also attain strong coupling to individual spin molecular qubits with potential applications to mediate qubit–qubit interactions or to implement qubit readout protocols.

Peach is a model for Prunus genetics and genomics, however, identifying and validating genes associated to peach breeding traits is a complex task. A gene coexpression network (GCN) capable of capturing stable gene–gene relationships would help researchers overcome the intrinsic limitations of peach genetics and genomics approaches and outline future research opportunities. In this study, we created four GCNs from 604 Illumina RNA-Seq libraries. We evaluated the performance of every GCN in predicting functional annotations using an algorithm based on the ‘guilty-by-association’ principle. The GCN with the best performance was COO300, encompassing 21 956 genes. To validate its performance predicting gene function, we performed two case studies. In case study 1, we used two genes involved in fruit flesh softening: the endopolygalacturonases PpPG21 and PpPG22. Genes coexpressing with both genes were extracted and referred to as melting flesh (MF) network. Finally, we performed an enrichment analysis of MF network and compared the results with the current knowledge regarding peach fruit softening. The MF network mostly included genes involved in cell wall expansion and remodeling, and with expressions triggered by ripening-related phytohormones, such as ethylene, auxin, and methyl jasmonate. In case study 2, we explored potential targets of the anthocyanin regulator PpMYB10.1 by comparing its gene-centered coexpression network with that of its grapevine orthologues, identifying a common regulatory network. These results validated COO300 as a powerful tool for peach and Prunus research. This network, renamed as PeachGCN v1.0, and the scripts required to perform a function prediction analysis are available at https://github.com/felipecobos/PeachGCN.

[Background] Intramuscular fat (IMF) content and its fatty acid (FA) composition are typically controlled by several genes, each with a small effect. In the current study, to pinpoint candidate genes and putative regulators involved in FA composition, we performed a multivariate integrative analysis between intramuscular FA and transcriptome profiles of porcine longissimus dorsi (LD) muscle. We also carried out a combination of network, regulatory impact factor (RIF), in silico prediction of putative target genes, and functional analyses to better support the biological relevance of our findings., [Results] For this purpose, we used LD RNA-Seq and intramuscular FA composition profiles of 129 Iberian × Duroc backcrossed pigs. We identified 378 correlated variables (13 FA and 365 genes), including six FA (C20:4n-6, C18:2n-6, C20:3n-6, C18:1n-9, C18:0, and C16:1n-7) that were among the most interconnected variables in the predicted network. The detected FA-correlated genes include genes involved in lipid and/or carbohydrate metabolism or in regulation of IMF deposition (e.g., ADIPOQ, CHUK, CYCS, CYP4B1, DLD, ELOVL6, FBP1, G0S2, GCLC, HMGCR, IDH3A, LEP, LGALS12, LPIN1, PLIN1, PNPLA8, PPP1R1B, SDR16C5, SFRP5, SOD3, SNW1, and TFRC), meat quality (GALNT15, GOT1, MDH1, NEU3, PDHA1, SDHD, and UNC93A), and transport (e.g., EXOC7 and SLC44A2). Functional analysis highlighted 54 over-represented gene ontology terms, including well-known biological processes and pathways that regulate lipid and carbohydrate metabolism. RIF analysis suggested a pivotal role for six transcription factors (CARHSP1, LBX1, MAFA, PAX7, SIX5, and TADA2A) as putative regulators of gene expression and intramuscular FA composition. Based on in silico prediction, we identified putative target genes for these six regulators. Among these, TADA2A and CARHSP1 had extreme RIF scores and present novel regulators in pigs. In addition, the expression of TADA2A correlated (either positively or negatively) with C20:4n-6, C18:2n-6, C20:3n-6, C18:1n-9, and that of CARHSP1 correlated (positively) with the C16:1n-7 lipokine. We also found that these two transcription factors share target genes that are involved in lipid metabolism (e.g., GOT1, PLIN1, and TFRC)., [Conclusions] This integrative analysis of muscle transcriptome and intramuscular FA profile revealed valuable information about key candidate genes and potential regulators for FA and lipid metabolism in pigs, among which some transcription factors are proposed to control gene expression and modulate FA composition differences.

Pedigree-based analyses’ prime role is to unravel relationships between individuals in breeding programs and germplasms. This is critical information for decoding the genetics underlying main inherited traits of relevance, and unlocking the genotypic variability of a species to carry out genomic selections and predictions. Despite the great interest, current lineage visualizations become quite limiting in terms of public display, exploration, and tracing of traits up to ancestral donors. PERSEUS is a user-friendly, intuitive, and interactive web-based tool for pedigree visualizations represented as directed graph networks distributed using a force-repulsion method. The visualizations do not only showcase individual relationships among accessions, but also facilitate a seamless search and download of phenotypic traits along the pedigrees. PERSEUS is a promising tool for breeders and scientists, advantageous for evolutionary, genealogy, and diversity analyses among related accessions and species.

Tempranillo red wines were partially dealcoholized (−3 v/v%) by osmotic distillation (OD) with membranes. First, polypropylene (PP) Liqui-Cel3M (3M) hollow fiber membrane modules were applied at 11 and 15 °C to study the effect of the removal of ethanol on the aroma of a certain wine. The influence of both temperatures was evaluated in terms of ethanol flux and aroma losses. Afterwards, two additional wines with different compositions were dealcoholized. The impact of the initial concentration of aromas on achieving a final product with an appealing aroma profile was studied, displaying the three wines a comparable aroma retention. Membrane OD was carried out with two additional hollow fiber membrane modules: another PP module (Zena) with a higher pore size, and a superhydrophobic PVDF module (Polymem). The latter gave rise to a partial dealcoholized wine with an aroma profile very similar to that of the pristine wine.

The structural phase transitions of Pr(Sr0.1Ca0.9)2Mn2O7 have been studied by synchrotron radiation x-ray powder diffraction. Three different charge order (CO) phases are identified as a function of temperature. The three phases have a checkerboard arrangement of compressed and expanded MnO6 octahedra in the perovskite bilayers. The structural changes associated with each transition are described in terms of the mode decomposition analysis with respect to the parent tetragonal structure. The high-temperature phase exhibits an orthorhombic symmetry (Amam) due to cooperative tilts of the MnO6 octahedra that can be ascribed to the irreducible representation (irrep) X3−. On cooling, the CO1 phase with Pbnm symmetry arises from the condensation of modes belonging to the irrep DT2 together with breathing (X1+) and antiferrodistortive (M5− and Y2) modes. The Mn site is split into two nonequivalent Mn atoms (Mn1 and Mn2) with a small charge segregation, and the asymmetric environment of Mn1 atoms form zigzag chains along the doubled b axis. Further cooling leads to the formation of the CO2 phase that comes from a relative change between the directions of previous X3− and DT2 distortions, producing the simultaneous condensation of new DT1 and ferrodistortive GM5− modes. In the CO2 structure (Am2m symmetry), Mn2 atoms are split into two nonequivalent sites but with similar oxidation states. Then the checkerboard arrangement between Mn1 and Mn2 atoms is preserved but with a reorientation of the zigzag chains along the a axis. At lower temperatures, the CO3 phase arises from a new direction change of irrep X3−, leading to the simultaneous condensation of new secondary modes. Its symmetry is Pn21m, and the Mn1 site is now split, which leads to a total of four nonequivalent Mn sites in the unit cell. In this phase, more tilts of the MnO6 octahedra are allowed following the a−b−c+ tilt schema.

Chromitite bodies can be found within ophiolitic mantle sections in three locations in Colombia: Medellín, Planeta Rica, and La Guajira. These chromitites are typically massive pods that are often surrounded by lateritic soil in Medellín and Planeta Rica, or small discoidal bodies in La Guajira. Inclusions in chromite are preserved to varying degrees in the three localities: olivine and pargasite are partially preserved in Medellín and Planeta Rica, whereas inclusions in La Guajira chromitites are completely altered to chlorite. Compositionally, chromite from the chromitites is high-Al in Medellín (Cr#[Cr/(Cr+Al) atomic ratio] = 0.41–0.51) and Planeta Rica (Cr# = 0.49–0.57), and high-Cr in La Guajira (Cr# = 0.75–0.76), whereas TiO contents are low in the three localities (0.12–0.43 wt%). Regarding trace elements composition, the chromitites are similar to others formed in supra-subduction zone settings; the chromite from the high-Al chromitites is similar to that in MORB/BABB, whereas chromite from the high-Cr chromitites has a strong boninitic affinity. Chromitites from Planeta Rica are richer in Ti, possibly due to the presence of nearby gabbroic bodies and impregnated peridotites. The alteration in chromite rims and silicate matrix is related to metamorphic processes. Bulk-rock platinum-group element (PGE) contents range from 30 to 487 ppb, and chondrite-normalized PGE patterns show the typical enrichment in IPGE relative to PPGE observed in most ophiolitic chromitites. The estimated melts in equilibrium with the different chromitites correspond to MORB-like melts for the Medellín and Planeta Rica chromitites and to boninites for La Guajira chromitites. However, the estimated TiO content in the melt is too low for a typical MORB, indicating back-arc basin basalts and a back-arc setting for the formation of the Medellín and Planeta Rica chromitites during the Late Triassic and the Late Jurassic, respectively. La Guajira chromitites are interpreted to have formed i

Volumetric loading is often a critical parameter in process design rather than weight. In this work, we have assessed the volumetric textural parameters of purified single-walled carbon nanotube materials (SWCNT). Purification is a necessary step in the SWCNT manufacturing process as they contain a metal residue inherent to their synthesis. Nitric acid treatment was applied for both metal removal and carbon structural/textural modification. Results show that the volumetric BET area is enhanced in ca. 500% with respect to the non-purified SWCNT (ca. 160% per mass), where both volumetric microporosity and external surfaces are enhanced. For such optimal material, the SWCNT structure remains well-defined though changes are observed (densification, more interstitial space, cutting of the tubes and amorphous carbon being formed). Three intrinsic factors contribute to the volumetric BET's enhancement: the bulk density and the mass-based surface parameters; microporous and external surfaces. The bulk density is enhanced due to a structural densification, thus more carbon is available per volume despite heavier metals (Ni, Y) being removed. One indirect factor, the MOx-removal effect, affects both intrinsic surface parameters. After studying this effect in depth, it was found that the microporosity is truly and largely enhanced due to newly-formed interstitial space. The external surface area is slightly improved but to a much lesser extent than microporosity. Overall, the factors dominating the volumetric BET for our system and applied experimental conditions are the bulk density, microporosity and MOx-removal effect. Concerning the conventional mass-based BET, microporosity and MOx-removal effect are the dominating factors. The study also reveals that mesoporosity control in these materials is possible, in comparison to previous studies.

[EN] Short informative video about breeding activities on Lathyrus spp. and Pisum sativum at Córdoba (Spain) for the development of new crop varieties adaptated to the dryland Mediterranean conditions., [ES] Video divulgativo breve sobre las actividades de Mejora en Lathyrus spp. y Pisum sativum en Córdoba (España) para el desarrollo de nuevas variedades adaptadas al secano Mediterráneo.

Genomic tools facilitate the efficient selection of improved genetic materials within a breeding program. Here, we focus on two apple fruit quality traits: shape and size. We utilized data from 11 fruit morphology parameters gathered across three years of harvest from 355 genotypes of the apple REFPOP collection, which serves as a representative sample of the genetic variability present in European-cultivated apples. The data were then employed for genome-wide association studies (GWAS) using the FarmCPU and the BLINK models. The analysis identified 59 SNPs associated with fruit size and shape traits (35 with FarmCPU and 45 with BLINK) responsible for 71 QTNs. These QTNs were distributed across all chromosomes except for chromosomes 10 and 15. Thirty-four QTNs, identified by 27 SNPs, were related for size traits, and 37 QTNs, identified by 26 SNPs, were related to shape attributes. The definition of the haploblocks containing the most relevant SNPs served to propose candidate genes, among them the genes of the ovate family protein MdOFP17 and MdOFP4 that were in a 9.7kb haploblock on Chromosome 11. RNA-seq data revealed low or null expression of these genes in the oblong cultivar “Skovfoged” and higher expression in the flat “Grand’mere.” The Gene Ontology enrichment analysis support a role of OFPs and hormones in shape regulation. In conclusion, this comprehensive GWAS analysis of the apple REFPOP collection has revealed promising genetic markers and candidate genes associated with apple fruit shape and size attributes, providing valuable insights that could enhance the efficiency of future breeding programs.

Upon storage, seeds inevitably age and lose their viability over time, which determines their longevity. Longevity correlates with successful seed germination and enhancing this trait is of fundamental importance for long-term seed storage (germplasm conservation) and crop improvement. Seed longevity is governed by a complex interplay between genetic factors and environmental conditions experienced during seed development and after-ripening that will shape seed physiology. Several factors have been associated with seed ageing such as oxidative stress responses, DNA repair enzymes, and composition of seed layers. Phytohormones, mainly abscisic acid, auxins, and gibberellins, have also emerged as prominent endogenous regulators of seed longevity, and their study has provided new regulators of longevity. Gaining a thorough understanding of how hormonal signalling genes and pathways are integrated with downstream mechanisms related to seed longevity is essential for formulating strategies aimed at preserving seed quality and viability. A relevant aspect related to research in seed longevity is the existence of significant differences between results depending on the seed equilibrium relative humidity conditions used to study seed ageing. Hence, this review delves into the genetic, environmental and experimental factors affecting seed ageing and longevity, with a particular focus on their hormonal regulation. We also provide gene network models underlying hormone signalling aimed to help visualize their integration into seed longevity and ageing. We believe that the format used to present the information bolsters its value as a resource to support seed longevity research for seed conservation and crop improvement.

Graphene oxide has been prepared from an industrial coke-like waste. The morphology of this material (GO-CW) is similar to that of standard graphene oxide (GO-G), although its surface has more defects. Both materials were used to prepare hybrid NHC-Ir(I)/graphene materials, consisting of molecular Ir(NHC) complexes covalently anchored to the graphene surface through the NHC moiety, following two different synthetic routes: (a) direct graphene electrografting of the previously synthesized aniline-functionalized imidazole-2-ylidene-Ir(I) complex, and (b) a two-step sequence comprising initial electrografting of aniline-imidazolium salts and subsequent chemical reaction with Ir(I) precursor anchoring imidazole-2-ylidene-Ir(I) molecular complexes. The synthesized NHC-Ir/graphene hybrid catalysts are active in the oxygen evolution reaction (OER) resulting in current densities in a similar range to those of other NHC-iridium(I) catalysts supported on GO. The highest activity corresponds to hybrid catalysts prepared by the two-step route, with even higher activity and stability when graphene oxide from industrial waste is used. EXAFS spectra of the materials prepared from both synthesis routes before oxidation catalysis reveal the local Ir coordination shell and a structural interaction between Ir and graphene. Both XANES and EXAFS spectra after electrocatalysis point to more oxidized species in which the molecular nature of the iridium catalysts is preserved.

Widespread tree growth decline and absence of acorn production are observed in formerly coppiced Quercus pyrenaica stands. Attempts to convert oak coppices into high forests by thinning have failed to date, possibly due to the massive root system developed by trees after centuries of coppicing. We tested root trenching and stem girdling as silvicultural treatments to mitigate this hypothetical root-to-shoot imbalance and enhance the physiological performance of multi-stemmed clonal trees. We expected that severing the roots within a clone by trenching would reduce root respiratory carbon losses. Alternatively, stem girdling would increase carbon availability above the girdled zone, whilst the communal root system is maintained by non-girdled stems. After clonal structure delineation in a one-hectare experimental plot, root trenching and stem girdling were applied to stems belonging to different clones. Twig hydraulic traits, leaf water potential, non-structural carbohydrates (NSC) concentration in twigs, stems and roots, stem xylem [CO2] as an indicator of root respiration, stem growth, and acorn production were discretely monitored up to 12 years after treatment application for comparison with control stems. Stem girdling led to short-term enhancements in NSC pools above the girdled zone. However, hydraulic dysfunction symptoms and canopy dieback were observed four years after girdling, eventually causing mortality. Root trenching initially increased root respiration and reduced stem growth without an apparent decline in the hydraulic function and NSC pools above-ground. Ten years after trenching, stem [NSC] increased while stem growth limitations diminished. Although not statistically significant, slight enhancements in acorn production were observed 6 and 12 years after trenching. We discourage stem girdling as a silvicultural practice to mitigate a root-to-shoot imbalance in abandoned oak coppices, as long-term detrimental effects outweighed potential benefits.

This study presents a sustainable microwave-assisted synthesis, based on the use of acetone and a water/acetic acid mixture instead of typical harmful DMF, to fabricate Zr-metal–organic frameworks (MOFs) UiO-66 and MOF-808 as fillers in a PIM-1 matrix for gas separation application. The mixed matrix membranes (MMMs) were prepared with varying loadings (2.5–10 wt%) of MOFs. The physicochemical properties (1H NMR, FTIR, XRD, N2 adsorption, TGA and SEM) of the resulting PIM-1, MOFs and MMMs were analyzed. The CO2/CH4 separation performance and membrane aging characteristics of the MMMs were evaluated. The incorporation of MOF fillers significantly improved CO2 permeability and CO2/CH4 selectivity, attributed to their CO2-philicity and narrow pore size (UiO-66 ≈ 0.6 nm and MOF-808 ≈ 1.8 nm). The MMMs with higher filler loadings (7.5 and 10 wt%) exhibited the most favorable separation performance. Due to the better crystallinity and textural properties, MOF-808 produced the best separation results at 10 wt% filler loading (a CO2/CH4 separation selectivity of 16.2 at 9090 Barrer of CO2 permeability). Aging led to a decrease in CO2 permeability but a slight increase in CO2/CH4 selectivity for all MMMs. Overall, the study highlights the potential of PIM-1/UiO-66 and PIM-1/MOF-808 MMMs as efficient materials for (CO2/CH4) separation comparing with the pristine PIM-1.

An in-depth understanding of corrosion inhibitor behaviour(s) at the metal–solution interface governed by unique molecular features is the key premise to realising molecular tailoring for pronounced metal protection. This study investigated the distinct adsorption behaviours induced by merely replacing the chemical functionality upon benzothiazole, i.e., 2-mercaptobenzothiazole (2-MBT) and 2-aminobenzothiazole (2-ABT), towards electro-galvanised steel (ZE) corrosion using both experimental and theoretical approaches. Electrochemical results confirm that both inhibitor candidates act as corrosion inhibitors for ZE in NaCl solution. The underlying interactions of the inhibitor molecule with the targeting metal, dissolved metal ions and corrosion products were explored by means of X-ray photoelectron spectroscopy, focused ion beam scanning electron microscopy and Raman spectroscopy. It is suggested that 2-MBT facilitates the precipitation upon the ZE by complexing with the released Zn2+ in solution, while 2-ABT promotes preferentially thin inhibitor film formation initiated by chemisorption. Density functional theory (DFT) reveals that at high concentrations the molecules tend to adsorb vertically (slightly tilted) at the surface, where the presented heteroatoms enhance surface–molecule interaction. In addition, DFT suggests that the strong binding strength of 2-MBT could facilitate the formation of complexes with displaced Zn. Based on the proposed mechanisms, the adsorption stability upon polarised ZE surfaces was determined, which reveals that 2-MBT forms a thick inhibitor layer at a relatively high polarisation state, whereas 2-ABT dissociates from the surface with the increasing value of surface overpotential. The findings of this study provide structural understanding that underpins inhibitor tailoring and molecular design to achieve the desired inhibition properties.

Global warming modulates the spatial and temporal occurrence of insect outbreaks, leading to as-yet-unknown effects on forests ecosystems. Warmer trends may favour the upward and northward expansion of pests, albeit increased exposure to heat events and droughts may also hamper insect growth and development. Thus far, further research is needed about the balance of climate warming on pine processionary moth (PPM) (Thaumetopoea pityocampa) development stages, especially at broader scales, despite being the main conifer-defoliating insect in the Mediterranean area. This research analyses the relationships of PPM with the climatic conditions during its most vulnerable development phases in Spain to provide base-information for forest managers. We hypothesize that warmer winter temperatures will increase PPM growth at their larval feeding stage, whereas summer-heat events will reduce PPM rates from egg and early larval stages, leading to counterbalanced effects of climate warming. Furthermore, we expect dry springs will allow an earlier development of PPM and higher incidence of outbreaks. To analyse climate effects on PPM populations in Andalusia, Castilla-La Mancha, and Navarre (37 to 42°N), we compiled information from the Regional Forest Services comprising up to 26 years of monitoring data from 2465 forest stands dominated by Pinus nigra and Pinus sylvestris. We fitted Cumulative Link Mixed Models (CLMM) to test the climate effects on four PPM defoliation severity levels. Our results support higher PPM larvae survival and incidence due to warmer winter conditions, but also the reduction of PPM population size under summer heat conditions. Particularly, the increasing incidence associated to warmer winters during the larval defoliating stage is counterbalanced by the decreasing population at earlier life stages during summer heat events. Spring drought also plays an important role on PPM incidence rates, but its effect is idiosyncratic to each region, suggesting an

Superglassy membranes synthesised by polymers of intrinsic microporosity (PIMs) suffer from physical aging and show poor gas permeance over time, especially thin membranes, due to the fast rearrangement of nonequilibrium polymer chains. Herein, we constructed a novel PIM-1 thin film nanocomposite membrane (TFN) using nanosized UiO-66−NH2 (≈10 nm)/carboxylated PIM-1 (cPIM-1) as the composite filler. Unlike conventional fillers, which interact with the polymer only via the surface, the UiO-66−NH2/cPIM-1 forms a stable three-dimensional (3D) network intertwining with the polymer chains, being very effective to impede chain relaxation, and thus physical aging. Nanosizing of UiO-66−NH2 was achieved by regulating the nucleation kinetics using carbon quantum dots (CQD) during the synthesis. This led to increased surface area, and hence more functional groups to bond with cPIM-1 (via hydrogen bonding between −NH2 and −COOH groups), which also improved interfacial compatibility between the 3D network and polymer chains avoiding defect formation. As a result, the novel TFN showed significantly improved performance in gas separation along with reduced aging (i.e. ≈6 % loss in CO2 permeability over 63 days); the aged membranes had a CO2 permeance of 2504 GPU and ideal selectivity values of 37.2 and 23.8 for CO2/N2 and CO2/CH4, respectively.

Molecular nanomagnets (MNMs), molecules containing interacting spins, have been a playground for quantum mechanics. They are characterized by many accessible low-energy levels that can be exploited to store and process quantum information. This naturally opens the possibility of using them as qudits, thus enlarging the tools of quantum logic with respect to qubit-based architectures. These additional degrees of freedom recently prompted the proposal for encoding qubits with embedded quantum error correction (QEC) in single molecules. QEC is the holy grail of quantum computing and this qudit approach could circumvent the large overhead of physical qubits typical of standard multi-qubit codes. Another important strength of the molecular approach is the extremely high degree of control achieved in preparing complex supramolecular structures where individual qudits are linked preserving their individual properties and coherence. This is particularly relevant for building quantum simulators, controllable systems able to mimic the dynamics of other quantum objects. The use of MNMs for quantum information processing is a rapidly evolving field which still requires to be fully experimentally explored. The key issues to be settled are related to scaling up the number of qudits/qubits and their individual addressing. Several promising possibilities are being intensively explored, ranging from the use of single-molecule transistors or superconducting devices to optical readout techniques. Moreover, new tools from chemistry could be also at hand, like the chiral-induced spin selectivity. In this paper, we will review the present status of this interdisciplinary research field, discuss the open challenges and envisioned solution paths which could finally unleash the very large potential of molecular spins for quantum technologies.

Ferrite nanoparticles serve as potent heterogeneous Fenton-like catalysts, producing reactive oxygen species (ROS) for decomposing organic pollutants. We investigated the impact of temperature and copper content on the catalytic activity of nanoparticles with different oxidation states of iron. Via solvothermal synthesis, we fabricated copper-doped magnetite (CuxFe3-xO4) with a Fe2+/Fe ratio ∼ 0.33 for the undoped system. Using a microwave-assisted method, we produced copper-doped oxidized ferrites, yielding a Fe2+/Fe ratio of ∼ 0.11 for the undoped nanoparticles. The ROS generated by the catalyst were identified and quantified by electron paramagnetic resonance, while optical spectroscopy allowed us to evaluate its effectiveness for the degradation of a model organic dye. At room temperature, the magnetite nanoparticles exhibited the most •OH radical production and achieved almost 90 % dye discoloration in 2 h. This efficiency decreased with increasing Cu concentration, concurrently with a decrease in •OH generation. Conversely, above room temperature, Cu-doped nanoparticles significantly enhance the dye degradation, reaching 100 % discoloration at 90 °C. This enhancement is accompanied by a systematic increase in the kinetic constants, obtained from reaction equations, with Cu doping. This study highlights the superior stability and high-temperature catalytic advantages of copper ferrite holding promise for enhancing the performance of nanocatalysts for decomposing organic contaminants.

Iron is critical during host–microorganism interactions1,2,3,4. Restriction of available iron by the host during infection is an important defence strategy, described as nutritional immunity5. However, this poses a conundrum for externally facing, absorptive tissues such as the gut epithelium or the plant root epidermis that generate environments that favour iron bioavailability. For example, plant roots acquire iron mostly from the soil and, when iron deficient, increase iron availability through mechanisms that include rhizosphere acidification and secretion of iron chelators6,7,8,9. Yet, the elevated iron bioavailability would also be beneficial for the growth of bacteria that threaten plant health. Here we report that microorganism-associated molecular patterns such as flagellin lead to suppression of root iron acquisition through a localized degradation of the systemic iron-deficiency signalling peptide Iron Man 1 (IMA1) in Arabidopsis thaliana. This response is also elicited when bacteria enter root tissues, but not when they dwell on the outer root surface. IMA1 itself has a role in modulating immunity in root and shoot, affecting the levels of root colonization and the resistance to a bacterial foliar pathogen. Our findings reveal an adaptive molecular mechanism of nutritional immunity that affects iron bioavailability and uptake, as well as immune responses.

We demonstrate the fabrication of sharp nanopillars of high aspect ratio onto specialized atomic force microscopy (AFM) microcantilevers and their use for high-speed AFM of DNA and nucleoproteins in liquid. The fabrication technique uses localized charged-particle-induced deposition with either a focused beam of helium ions or electrons in a helium ion microscope (HIM) or scanning electron microscope (SEM). This approach enables customized growth onto delicate substrates with nanometer-scale placement precision and in situ imaging of the final tip structures using the HIM or SEM. Tip radii of <10 nm are obtained and the underlying microcantilever remains intact. Instead of the more commonly used organic precursors employed for bio-AFM applications, we use an organometallic precursor (tungsten hexacarbonyl) resulting in tungsten-containing tips. Transmission electron microscopy reveals a thin layer of carbon on the tips. The interaction of the new tips with biological specimens is therefore likely very similar to that of standard carbonaceous tips, with the added benefit of robustness. A further advantage of the organometallic tips is that compared to carbonaceous tips they better withstand UV–ozone cleaning treatments to remove residual organic contaminants between experiments, which are inevitable during the scanning of soft biomolecules in liquid. Our tips can also be grown onto the blunted tips of previously used cantilevers, thus providing a means to recycle specialized cantilevers and restore their performance to the original manufacturer specifications. Finally, a focused helium ion beam milling technique to reduce the tip radii and thus further improve lateral spatial resolution in the AFM scans is demonstrated.

We lack understanding of how variable is radial growth of coexisting tree and shrub species, and how growth is constrained by drought depending on site aridity. Here, we compared the radial growth of two widespread and coexisting species, a winter deciduous shrub (Amelanchier ovalis Medik.) and an evergreen conifer tree (Pinus sylvestris L.). We sampled four sites in Northeastern Spain subjected to different aridity levels and used dendrochronological methods to quantify growth patterns and responses to climate variables. The growth of the two species varied between regions, being lower in the driest sites. The first-order autocorrelation (growth persistence) was higher in more mesic sites but without clear differences between species. Tree and shrub growth negatively responded to elevated summer temperatures and positively to spring-summer precipitation and wet conditions. However, negative growth responses of the shrub to drought were only observed in the two driest sites in contrast to widespread responses of the tree. Abrupt growth reductions were common in the drier sites, but resilience indices show that the two species rapidly recovered pre-drought growth levels. The lower growth synchrony of the shrub as compared to the tree can be due to the multistemmed architecture, fast growth and low stature of the shrub. Besides, the high dependency of the shrub growth on summer rainfall can explain why drought limitations were only apparent in the two driest sites. In any case, results point out to the dendrochronological potential of shrubs, which is particularly relevant giving its ability to inhabit woodlands and treeless regions under harsh climatic conditions. Nevertheless, further research is required to elucidate the capacity of shrub species to tolerate drought, as well as to understand how shrubs thrive in water- and cold-limited environments.

The endophytic fungus Aspergillus sp. SPH2 was isolated from the stems of the endemic plant Bethencourtia palmensis and its extracts were found to have strong fungicidal effects against Botrytis cinerea and ixodicidal effects against Hyalomma lusitanicum at different fermentation times. In this study, the fungus was grown using three different culture media and two methodologies, Microparticulate Enhancement Cultivation (MPEC) and Semi-Solid-State Fermentation (Semi-SSF), to increase the production of secondary metabolites during submerged fermentation. The addition of an inert support to the culture medium (Semi-SSF) resulted in a significant increase in the extract production. However, when talcum powder was added to different culture media, unexpected results were observed, with a decrease in the production of the biocompounds of interest. Metabolomic analyses showed that the production of aspergillic, neoaspergillic, and neohydroxyaspergillic acids peaked in the first few days of fermentation, with notable differences observed among the methodologies and culture media. Mellein production was particularly affected by the addition of an inert support to the culture medium. These results highlight the importance of surface properties and morphology of spores and mycelia during fermentation by this fungal species.

We fabricated ferromagnetic nano-crystalline thin films of Co, Fe, Co–Fe and Co-rich and Fe-rich, Co–MT and Fe–MT (MT = transition metal), constituted by nano-sheets with a controlled slant. Visualization of these nano-sheets by Scanning Tunneling Microscopy and High-Resolution Transmission Electron Microscopy (HRTEM) showed typically tilt angles ≈56° with respect to the substrate plane, and nano-sheets ≈3.0–4.0 nm thick, ≈30–100 nm wide, and ≈200–300 nm long, with an inter-sheet distance of ≈0.9–1.2 nm, depending on their constitutive elements. Induced by this nano-morphology, these films exhibited large uniaxial magnetic anisotropy in the plane, the easy direction of magnetization being parallel to the longitudinal direction of the nano-sheets. In the as-grown films, typical values of the anisotropy field were between Hk ≈ 48 and 110 kA/m depending on composition. The changes in the nano-morphology caused by thermal treatments, and hence in the anisotropic properties, were also visualized by HRTEM, including chemical analysis at the nano-scale. Some films retained their nano-sheet morphology and increased their anisotropies by up to three times after being heated to at least 500 °C: for example, the thermal treatments produced crystallization processes and the growth of CoV and CoFe magnetic phases, maintaining the nano-sheet morphology. In contrast, other annealed films, Co, Fe, CoZn, CoCu… lost their nano-sheet morphology and hence their anisotropies. This work opens a path of study for these new magnetically anisotropic materials, particularly with respect to the nano-morphological and structural changes related to the increase in magnetic anisotropy.